CN109836956B - Preparation method of water-based epoxy anti-rust primer - Google Patents
Preparation method of water-based epoxy anti-rust primer Download PDFInfo
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- CN109836956B CN109836956B CN201810347489.8A CN201810347489A CN109836956B CN 109836956 B CN109836956 B CN 109836956B CN 201810347489 A CN201810347489 A CN 201810347489A CN 109836956 B CN109836956 B CN 109836956B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000004593 Epoxy Substances 0.000 title claims abstract description 33
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 56
- 239000000835 fiber Substances 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 239000013556 antirust agent Substances 0.000 claims abstract description 24
- 239000002121 nanofiber Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000010445 mica Substances 0.000 claims abstract description 11
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 40
- 238000005303 weighing Methods 0.000 claims description 39
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 polysiloxane Polymers 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000003729 cation exchange resin Substances 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 14
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052912 lithium silicate Inorganic materials 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000003860 storage Methods 0.000 description 6
- 241001330002 Bambuseae Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of a water-based epoxy anti-rust primer, and belongs to the technical field of paint preparation. The invention firstly carries out surface treatment on the nano-fiber, then loads water-based antirust agent lithium silicate on the nano-fiber to obtain a modified fiber antirust agent, modifies epoxy resin by using a modified fiber antirust agent and monomer mixed liquid to obtain a modified water-based epoxy resin emulsion, finally mixes and grinds the water-based epoxy resin emulsion, water, mica powder and other substances to obtain a component A, and mixes a curing agent which is a component B when in use to obtain the water-based epoxy antirust primer.
Description
Technical Field
The invention belongs to the technical field of paint preparation, and particularly relates to a preparation method of a water-based epoxy anti-rust primer.
Background
The antirust paint is formed by coating a layer of anticorrosive coating with good compactness and adhesion on the surface of a metal base material, so that a corrosive medium (moisture, oxygen, corrosive ions and the like) is prevented from directly contacting the metal base material, the generation of corrosive current is inhibited, and the antirust effect of the metal is achieved. At present, the traditional antirust paint not only contains a large amount of volatile organic solvents, but also contains a plurality of toxic pigments and fillers, and the wide use of the traditional antirust paint causes great pollution to the environment. With the enhancement of environmental awareness, people pay more and more attention to the environmental protection problem of the protective coating, so that the paint industry is promoted to develop towards low toxicity/non-toxicity and little pollution to the environment. Therefore, the water-based rust inhibitive paint is an important development direction of the rust inhibitive paint.
Among them, the water-based epoxy rust-inhibiting primer is widely used in the heavy-duty anticorrosion fields of ships, inner and outer walls of pipelines, mine steel frames, airplanes, high-speed trains and the like. Earlier people generally made epoxy emulsions by mechanical and phase inversion methods. Namely, a water-insoluble epoxy resin is dispersed in water in a particulate state by means of a high-speed stirring apparatus in the presence of an emulsifier. The two methods have simple process, but have a plurality of defects, and the obtained emulsion has larger particle size, irregular particle shape, wide size distribution, poor emulsion stability and the like.
However, the water-based epoxy resin is a thermodynamically unstable system, the storage stability is poor and the comprehensive performance of the coating is unsatisfactory, so that the water resistance and the rust resistance of the water-based epoxy resin coating are poor and the performance requirement of the rust-resistant coating can not be met.
At present, the contradiction between the storage stability of the aqueous dispersion of the aqueous antirust paint and the water resistance and corrosion resistance of the coating film of the dispersion is a big bottleneck for restricting the development of the aqueous epoxy resin antirust paint. Therefore, research and development of water-based antirust paint which has good storage stability, excellent coating film and corrosion resistance is urgent, and considerable economic and social benefits are achieved.
In conclusion, the technical key for popularizing and applying the water-based epoxy anti-rust primer is to solve the problems.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects that the water-based epoxy resin coating has poor water resistance and poor antirust performance and cannot meet the performance requirement of an antirust coating due to poor storage stability and unsatisfactory comprehensive performance of the coating, the preparation method of the water-based epoxy antirust primer is provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
(1) weighing nano-fibers, adding the nano-fibers into an ethanol solution of ammonia, soaking, then carrying out suction filtration, collecting filter residues, washing with absolute ethyl alcohol and water in sequence, and then drying to obtain surface-treated nano-fibers;
(2) preparing a lithium nitrate solution with the mass fraction of 5%, weighing the nanofiber, the lithium nitrate solution and disodium ethylene diamine tetraacetate with the surface treated according to the mass ratio of 5-10: 30-50: 1-2, stirring and mixing for 20-30 min, then dropwise adding an active silicic acid solution, continuously stirring for 1-2 h, standing at room temperature for 5-7 h, standing, then putting into an oven for drying, putting into a tubular furnace after obtaining a dried substance, heating to 400-500 ℃ under the protection of nitrogen atmosphere, preserving heat, calcining, then adding into a pulverizer for pulverizing, and sieving with a 500-mesh sieve to obtain a modified fiber antirust agent;
(3) weighing epoxy resin and absolute ethyl alcohol, filling the epoxy resin and the absolute ethyl alcohol into a three-neck flask, stirring and mixing for 30-40 min, adding phosphoric acid, heating to reflux, performing reflux reaction for 1-2 h, adding a monomer mixed solution, a fiber antirust agent and an initiator, heating to 105-120 ℃, stirring and reacting for 3-4 h, cooling to 60-70 ℃, adjusting a reaction system to be neutral, adding water, stirring at a rotating speed of 1200-2000 r/min for 30-40 min, cooling to room temperature after stirring, and discharging to obtain a modified water-based epoxy resin emulsion;
(4) respectively weighing and mixing the modified waterborne epoxy resin emulsion, water, mica powder, aluminum tripolyphosphate, magnesium humate, a dispersing agent, a defoaming agent, a wetting agent, a leveling agent and magnesium humate, uniformly mixing, adding into a grinding machine for grinding, and sieving by a filter screen of 80-100 meshes to obtain a component A, wherein a curing agent is a component B;
(5) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
In the step (1), the nano fiber is one of polyimide fiber, polyester fiber, hemp fiber, bamboo fiber or carbon fiber.
The adding amount of the active silicic acid solution in the step (2) is 1-1.5 times of the mass of the lithium nitrate solution; the preparation method of the active silicic acid solution comprises the following steps: preparing a sodium silicate aqueous solution with the mass fraction of 3%, performing exchange reaction by using cation exchange resin, and collecting to obtain an active silicic acid solution.
The epoxy resin in the step (3) is one of E51 epoxy resin, E44 epoxy resin or E42 epoxy resin.
The monomer mixed solution in the step (3) is as follows: according to the mass ratio of 3: 1: 1, weighing methacrylic acid, butyl acrylate and styrene, adding into absolute ethyl alcohol, and uniformly stirring and mixing to obtain a monomer mixed solution; the initiator is ammonium persulfate or potassium persulfate.
Weighing 50-70 parts of modified water-based epoxy resin emulsion, 10-20 parts of water, 1-5 parts of mica powder, 1-3 parts of aluminum tripolyphosphate, 0.3-0.5 part of dispersing agent, 0.5-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 0.1-0.2 part of flatting agent, 0.1-0.3 part of magnesium humate and 12-20 parts of curing agent according to parts by weight.
The dispersant is SN-5029 dispersant or dispersant X-3204; the defoaming agent is an A-10 defoaming agent or an SN-1311 defoaming agent; the wetting agent is BYK-346; the leveling agent is polyether modified polysiloxane; the curing agent is formed by mixing polysebacic anhydride and polyazelaic anhydride according to the mass ratio of 1: 3.
Compared with other methods, the method has the beneficial technical effects that:
(1) the modified fiber antirust agent is obtained by loading lithium silicate on the surface of the nanofiber, has stable property, is non-toxic and harmless, is an excellent water-based antirust agent, is uniformly and stably dispersed in water-based epoxy resin after being added into water-based epoxy resin emulsion, can be filled into holes and defects of a coating, forms a compact physical isolation layer which is superposed layer by layer, is crosslinked with the epoxy resin under the action of an initiator, and enhances the interaction between fiber and a resin matrix interface as active hydroxyl on the surface of the fiber and the crosslinking network of the epoxy resin generate intermolecular hydrogen bonds;
(2) according to the invention, methacrylic acid, butyl acrylate and styrene are used as monomers to prepare a monomer mixed solution, hydrophilic groups can be introduced into an epoxy resin molecular chain through chemical grafting after the monomer mixed solution is added, and stable dispersion of epoxy resin in water is realized after neutralization and salt formation;
(3) after the water-based epoxy anti-rust primer prepared by the invention is used, phosphate ions and tripolyphosphate ions can be dissociated from the coating and form a compact attached film with base metal ions, so that rusting is inhibited, and mica is selected as a filler, so that the permeability of water and oxygen in the air to a paint film can be effectively slowed down, and the anti-rust purpose is achieved;
(4) the water-based epoxy anti-rust primer prepared by the invention has good storage stability and film-forming property, and the paint film has excellent water resistance, salt spray resistance and anti-rust property, the salt spray resistance can reach more than 1600 hours, and the water-based epoxy anti-rust primer is beneficial to protecting the substrate by the paint film.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1
The method comprises the following steps: preparation of modified fiber antirust agent
(1) Weighing 50g of polyimide nano fiber, adding the polyimide nano fiber into 200g of ethanol solution containing 5% ammonia by mass, soaking, carrying out suction filtration after 30min, collecting filter residue, washing with absolute ethyl alcohol and water in sequence, and drying to obtain the nano fiber after surface treatment;
(2) preparing a sodium silicate aqueous solution with the mass fraction of 3%, performing exchange reaction by using cation exchange resin, and collecting to obtain an active silicic acid solution;
(3) preparing a lithium nitrate solution with the mass fraction of 5%, weighing the nano-fiber, the lithium nitrate solution and the disodium ethylene diamine tetraacetate with the surface treated according to the mass ratio of 5:30:1, stirring and mixing for 20min, then dropwise adding an active silicic acid solution with the mass of 1 time of that of the lithium nitrate solution, continuously stirring for 1h, standing at room temperature for 5h, drying in a drying oven after standing to obtain a dried substance, then placing in a tubular furnace, heating to 400 ℃ under the protection of nitrogen atmosphere, preserving heat, calcining, then adding in a pulverizer for pulverizing, and sieving with a 500-mesh sieve to obtain the modified fiber antirust agent;
step two: modified aqueous epoxy resin emulsion
(1) According to the mass ratio of 3: 1: 1, weighing methacrylic acid, butyl acrylate and styrene, adding into absolute ethyl alcohol, and uniformly stirring and mixing to obtain a monomer mixed solution;
(2) weighing 60g of epoxy resin E51 and 200g of absolute ethyl alcohol, placing the epoxy resin E51 and the absolute ethyl alcohol into a three-neck flask, stirring and mixing for 30min, adding 4g of phosphoric acid, heating to reflux, adding 8g of monomer mixed solution, 3g of fiber antirust agent and 1g of ammonium persulfate after reflux reaction for 1h, heating to 105 ℃, stirring and reacting for 3h, cooling to 60 ℃, adjusting the reaction system to be neutral, adding 30g of water, stirring for 30min at the rotating speed of 1200r/min, stirring, cooling to room temperature, and discharging to obtain the modified waterborne epoxy resin emulsion.
Step three: preparation of aqueous epoxy antirust primer
(1) Weighing 100g of modified waterborne epoxy resin emulsion, 20g of water, 2g of mica powder, 2g of aluminum tripolyphosphate, 0.6g of dispersing agent SN-5029, 1g of defoaming agent A-10, 1g of wetting agent BYK-346, 0.2g of polyether modified polysiloxane and 0.2g of magnesium humate, uniformly mixing, adding into a grinder for grinding, and sieving by a 80-mesh filter screen to obtain a component A; weighing 6g of polysebacic anhydride and 18g of polyazelaic anhydride, mixing and stirring uniformly to obtain a component B;
(2) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
Example 2
The method comprises the following steps: preparation of modified fiber antirust agent
(1) Weighing 60g of nano bamboo fiber, adding the nano bamboo fiber into 225g of ethanol solution containing 5% by mass of ammonia, soaking, carrying out suction filtration after 40min, collecting filter residue, washing with absolute ethyl alcohol and water in sequence, and drying to obtain surface-treated nano fiber;
(2) preparing a sodium silicate aqueous solution with the mass fraction of 3%, performing exchange reaction by using cation exchange resin, and collecting to obtain an active silicic acid solution;
(3) preparing a lithium nitrate solution with the mass fraction of 5%, weighing the nano-fiber, the lithium nitrate solution and the disodium ethylene diamine tetraacetate with the surface treated according to the mass ratio of 7:40:1, stirring and mixing for 25min, then dropwise adding an active silicic acid solution which is 1.3 times of the mass of the lithium nitrate solution, continuously stirring for 1.5h, standing at room temperature for 6h, standing, then putting into a drying oven for drying to obtain a dried substance, then putting into a tubular furnace, heating to 450 ℃ under the protection of nitrogen atmosphere, preserving heat, calcining, then adding into a pulverizer for pulverizing, and sieving with a 500-mesh sieve to obtain a modified fiber antirust agent;
step two: modified aqueous epoxy resin emulsion
(1) According to the mass ratio of 3: 1: 1, weighing methacrylic acid, butyl acrylate and styrene, adding into absolute ethyl alcohol, and uniformly stirring and mixing to obtain a monomer mixed solution;
(2) weighing 70g of epoxy resin E44 and 230g of absolute ethyl alcohol, putting into a three-neck flask, stirring and mixing for 35min, adding 6g of phosphoric acid, heating to reflux, adding 10g of monomer mixed solution, 4g of fiber antirust agent and 2g of potassium persulfate after reflux reaction for 1.5h, heating to 110 ℃, stirring and reacting for 3.5h, cooling to 65 ℃, adding 40g of water after adjusting a reaction system to be neutral, stirring for 35min at a rotating speed of 1600r/min, stirring, cooling to room temperature, and discharging to obtain the modified waterborne epoxy resin emulsion.
Step three: preparation of aqueous epoxy antirust primer
(1) Weighing 120g of modified waterborne epoxy resin emulsion, 30g of water, 5g of mica powder, 4g of aluminum tripolyphosphate, 0.8g of dispersing agent SN-5029, 1.5g of defoaming agent SN-1311, 1.5g of wetting agent BYK-346, 0.3g of polyether modified polysiloxane and 0.4g of magnesium humate, uniformly mixing, adding into a grinding machine for grinding, and sieving by a 80-mesh filter screen to obtain a component A; weighing 8g of polysebacic anhydride and 24g of polyazelaic anhydride, mixing and stirring uniformly to obtain a component B;
(2) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
Example 3
The method comprises the following steps: preparation of modified fiber antirust agent
(1) Weighing 70g of carbon nanofiber, adding the carbon nanofiber into 250g of ethanol solution containing 5% by mass of ammonia, soaking, carrying out suction filtration after 50min, collecting filter residues, washing with absolute ethyl alcohol and water in sequence, and drying to obtain surface-treated nanofiber;
(2) preparing a sodium silicate aqueous solution with the mass fraction of 3%, performing exchange reaction by using cation exchange resin, and collecting to obtain an active silicic acid solution;
(3) preparing a lithium nitrate solution with the mass fraction of 5%, weighing the nano-fiber, the lithium nitrate solution and the disodium ethylene diamine tetraacetate with the surface treated according to the mass ratio of 10:50:2, stirring and mixing for 30min, then dropwise adding an active silicic acid solution which is 1.5 times of the mass of the lithium nitrate solution, continuously stirring for 2h, standing for 7h at room temperature, drying in a drying oven after standing to obtain a dried substance, then putting in a tubular furnace, heating to 500 ℃ under the protection of nitrogen atmosphere, preserving heat, calcining, adding in a pulverizer for pulverizing, and sieving with a 500-mesh sieve to obtain the modified fiber antirust agent;
step two: modified aqueous epoxy resin emulsion
(1) According to the mass ratio of 3: 1: 1, weighing methacrylic acid, butyl acrylate and styrene, adding into absolute ethyl alcohol, and uniformly stirring and mixing to obtain a monomer mixed solution;
(2) weighing 80g of epoxy resin E42 and 250g of absolute ethyl alcohol, putting into a three-neck flask, stirring and mixing for 40min, adding 8g of phosphoric acid, heating to reflux, adding 12g of monomer mixed solution, 5g of fiber antirust agent and 3g of ammonium persulfate after reflux reaction for 2h, heating to 120 ℃, stirring and reacting for 4h, cooling to 70 ℃, adding 50g of water after adjusting a reaction system to be neutral, stirring for 40min at a rotating speed of 2000r/min, cooling to room temperature after stirring, and discharging to obtain the modified waterborne epoxy resin emulsion.
Step three: preparation of aqueous epoxy antirust primer
(1) Weighing 140g of modified waterborne epoxy resin emulsion, 40g of water, 10g of mica powder, 6g of aluminum tripolyphosphate, 1.0g of dispersant X-3204, 2g of defoamer SN-1311, 2g of wetting agent BYK-346, 0.4g of polyether modified polysiloxane and 0.6g of magnesium humate, uniformly mixing, adding into a grinder for grinding, and sieving by a 80-mesh filter screen to obtain a component A; weighing 10g of polysebacic anhydride and 30g of polyazelaic anhydride, mixing and stirring uniformly to obtain a component B;
(2) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
Comparative example 1
Compared with the example 1, the modified fiber antirust agent is not prepared, the modified fiber antirust agent is not added into the modified water-based epoxy resin emulsion, and the rest operation steps are unchanged;
the method comprises the following steps: modified aqueous epoxy resin emulsion
(1) According to the mass ratio of 3: 1: 1, weighing methacrylic acid, butyl acrylate and styrene, adding into absolute ethyl alcohol, and uniformly stirring and mixing to obtain a monomer mixed solution;
(2) weighing 70g of epoxy resin E44 and 230g of absolute ethyl alcohol, putting into a three-neck flask, stirring and mixing for 35min, adding 6g of phosphoric acid, heating to reflux, adding 10g of monomer mixed solution and 2g of potassium persulfate after reflux reaction for 1.5h, heating to 110 ℃, stirring and reacting for 3.5h, cooling to 65 ℃, adjusting the reaction system to be neutral, adding 40g of water, stirring for 35min at a rotating speed of 1600r/min, stirring, cooling to room temperature, and discharging to obtain the modified waterborne epoxy resin emulsion.
Step two: preparation of aqueous epoxy antirust primer
(1) Weighing 120g of modified waterborne epoxy resin emulsion, 30g of water, 5g of mica powder, 4g of aluminum tripolyphosphate, 0.8g of dispersing agent SN-5029, 1.5g of defoaming agent SN-1311, 1.5g of wetting agent BYK-346, 0.3g of polyether modified polysiloxane and 0.4g of magnesium humate, uniformly mixing, adding into a grinding machine for grinding, and sieving by a 80-mesh filter screen to obtain a component A; weighing 10g of polysebacic anhydride and 30g of polyazelaic anhydride, mixing and stirring uniformly to obtain a component B;
(2) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
Comparative example 2
Compared with the embodiment 2, the monomer mixed solution is not added into the modified waterborne epoxy resin emulsion, but the emulsifier is added, and the operation steps are as follows;
the method comprises the following steps: preparation of modified fiber antirust agent
(1) Weighing 60g of nano bamboo fiber, adding the nano bamboo fiber into 225g of ethanol solution containing 5% by mass of ammonia, soaking, carrying out suction filtration after 40min, collecting filter residue, washing with absolute ethyl alcohol and water in sequence, and drying to obtain surface-treated nano fiber;
(2) preparing a sodium silicate aqueous solution with the mass fraction of 3%, performing exchange reaction by using cation exchange resin, and collecting to obtain an active silicic acid solution;
(3) preparing a lithium nitrate solution with the mass fraction of 5%, weighing the nano-fiber, the lithium nitrate solution and the disodium ethylene diamine tetraacetate with the surface treated according to the mass ratio of 7:40:1, stirring and mixing for 25min, then dropwise adding an active silicic acid solution which is 1.3 times of the mass of the lithium nitrate solution, continuously stirring for 1.5h, standing at room temperature for 6h, standing, then putting into a drying oven for drying to obtain a dried substance, then putting into a tubular furnace, heating to 450 ℃ under the protection of nitrogen atmosphere, preserving heat, calcining, then adding into a pulverizer for pulverizing, and sieving with a 500-mesh sieve to obtain a modified fiber antirust agent;
step two: modified aqueous epoxy resin emulsion
(1) Weighing 70g of epoxy resin E44 and 230g of absolute ethyl alcohol, filling the epoxy resin E44 and the absolute ethyl alcohol into a three-neck flask, stirring and mixing for 35min, adding 6g of phosphoric acid, heating to reflux, adding 4g of fiber antirust agent, 8g of sodium dodecyl sulfate and 2g of potassium persulfate after reflux reaction for 1.5h, cooling to 70 ℃, stirring and reacting for 2h, adding water after reaction, stirring for 30min at the rotating speed of 3000r/min, cooling to room temperature after stirring, and discharging to obtain the modified waterborne epoxy resin emulsion.
Step three: preparation of aqueous epoxy antirust primer
(1) Weighing 120g of modified waterborne epoxy resin emulsion, 30g of water, 5g of mica powder, 4g of aluminum tripolyphosphate, 0.8g of dispersing agent SN-5029, 1.5g of defoaming agent SN-1311, 1.5g of wetting agent BYK-346, 0.3g of polyether modified polysiloxane and 0.4g of magnesium humate, uniformly mixing, adding into a grinding machine for grinding, and sieving by a 80-mesh filter screen to obtain a component A; weighing 8g of polysebacic anhydride and 24g of polyazelaic anhydride, mixing and stirring uniformly to obtain a component B;
(2) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
The examples 1 to 3 and comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in Table 1.
Table 1:
as can be seen from the data in Table 1, the waterborne epoxy anti-rust primers prepared by the method of the invention in examples 1-3 have excellent adhesion, water resistance, storage stability and other properties, while the modified fiber anti-rust agent is not added in comparative example 1, the water resistance and the salt spray resistance are poor, while the waterborne epoxy emulsion prepared by the emulsification method with the emulsifier is used in comparative example 2, and the emulsion breaking and delamination phenomenon occurs after the emulsion is stored for 12 months.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all such changes or substitutions should be covered by the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A preparation method of a water-based epoxy anti-rust primer is characterized by comprising the following specific preparation steps:
(1) weighing nano-fibers, adding the nano-fibers into an ethanol solution of ammonia, soaking, then carrying out suction filtration, collecting filter residues, washing with absolute ethyl alcohol and water in sequence, and then drying to obtain surface-treated nano-fibers;
(2) preparing a lithium nitrate solution with the mass fraction of 5%, weighing the nanofiber, the lithium nitrate solution and disodium ethylene diamine tetraacetate with the surface treated according to the mass ratio of 5-10: 30-50: 1-2, stirring and mixing for 20-30 min, then dropwise adding an active silicic acid solution, continuously stirring for 1-2 h, standing at room temperature for 5-7 h, standing, then putting into an oven for drying, putting into a tubular furnace after obtaining a dried substance, heating to 400-500 ℃ under the protection of nitrogen atmosphere, preserving heat, calcining, crushing, and sieving with a 500-mesh sieve to obtain a modified fiber antirust agent;
(3) weighing epoxy resin and absolute ethyl alcohol, filling the epoxy resin and the absolute ethyl alcohol into a three-neck flask, stirring and mixing for 30-40 min, adding phosphoric acid, heating to reflux, performing reflux reaction for 1-2 h, adding a monomer mixed solution, a modified fiber antirust agent and an initiator, heating to 105-120 ℃, stirring and reacting for 3-4 h, cooling to 60-70 ℃, adjusting a reaction system to be neutral, adding water, stirring at a rotating speed of 1200-2000 r/min for 30-40 min, cooling to room temperature after stirring, and discharging to obtain a modified water-based epoxy resin emulsion;
(4) respectively weighing and mixing the modified waterborne epoxy resin emulsion, water, mica powder, aluminum tripolyphosphate, a dispersing agent, a defoaming agent, a wetting agent, a flatting agent and magnesium humate, uniformly mixing, adding into a grinding machine for grinding, and passing through a filter screen of 80-100 meshes after grinding to obtain a component A, wherein a curing agent is a component B;
(5) and respectively packaging the component A and the component B, mixing when in use, and uniformly mixing to obtain the water-based epoxy antirust primer.
2. The method for preparing the water-based epoxy rust inhibitive primer according to claim 1, characterized in that: in the step (1), the nano fiber is one of polyimide fiber, polyester fiber, hemp fiber, bamboo fiber or carbon fiber.
3. The method for preparing the water-based epoxy rust inhibitive primer according to claim 1, characterized in that: the adding amount of the active silicic acid solution in the step (2) is 1-1.5 times of the mass of the lithium nitrate solution; the preparation method of the active silicic acid solution comprises the following steps: preparing a sodium silicate aqueous solution with the mass fraction of 3%, performing exchange reaction by using cation exchange resin, and collecting to obtain an active silicic acid solution.
4. The method for preparing the water-based epoxy rust inhibitive primer according to claim 1, characterized in that: the epoxy resin in the step (3) is one of E51 epoxy resin, E44 epoxy resin or E42 epoxy resin.
5. The method for preparing the water-based epoxy rust inhibitive primer according to claim 1, characterized in that: the monomer mixed solution in the step (3) is as follows: according to the mass ratio of 3: 1: 1, weighing methacrylic acid, butyl acrylate and styrene, adding into absolute ethyl alcohol, and uniformly stirring and mixing to obtain a monomer mixed solution; the initiator is ammonium persulfate or potassium persulfate.
6. The method for preparing the water-based epoxy rust inhibitive primer according to claim 1, characterized in that: weighing 50-70 parts of modified water-based epoxy resin emulsion, 10-20 parts of water, 1-5 parts of mica powder, 1-3 parts of aluminum tripolyphosphate, 0.3-0.5 part of dispersing agent, 0.5-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 0.1-0.2 part of flatting agent, 0.1-0.3 part of magnesium humate and 12-20 parts of curing agent according to parts by weight.
7. The method for preparing the water-based epoxy rust inhibitive primer according to claim 1 or 6, characterized in that: the dispersant is SN-5029 dispersant or dispersant X-3204; the defoaming agent is an A-10 defoaming agent or an SN-1311 defoaming agent; the wetting agent is BYK-346; the leveling agent is polyether modified polysiloxane; the curing agent is formed by mixing polysebacic anhydride and polyazelaic anhydride according to the mass ratio of 1: 3.
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| CN102782055A (en) * | 2010-02-26 | 2012-11-14 | 新日本制铁株式会社 | Corrosion-proofing coating composition and process for production thereof, and method for prevention of corrosion in steel material |
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| CN103972501A (en) * | 2014-03-03 | 2014-08-06 | 南昌大学 | Preparation method of high-purity lithium silicate material |
| CN105086770A (en) * | 2015-09-17 | 2015-11-25 | 浙江钱浪涂料科技有限公司 | Iron oxide red water-based epoxy rust-proof primer and preparing method thereof |
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| US6596406B2 (en) * | 2000-12-28 | 2003-07-22 | Nitto Denko Corporation | Wiring board prepreg and manufacturing method thereof |
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| CN102782055A (en) * | 2010-02-26 | 2012-11-14 | 新日本制铁株式会社 | Corrosion-proofing coating composition and process for production thereof, and method for prevention of corrosion in steel material |
| CN103342939A (en) * | 2013-06-27 | 2013-10-09 | 天长市巨龙车船涂料有限公司 | Water-soluble epoxy ester antirust paint |
| CN103972501A (en) * | 2014-03-03 | 2014-08-06 | 南昌大学 | Preparation method of high-purity lithium silicate material |
| CN105086770A (en) * | 2015-09-17 | 2015-11-25 | 浙江钱浪涂料科技有限公司 | Iron oxide red water-based epoxy rust-proof primer and preparing method thereof |
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Address after: 213164 No.205, Fenglin South Road, Wujin national high tech Industrial Development Zone, Changzhou City, Jiangsu Province Patentee after: Jiangsu Jinhua heavy anticorrosive coating Co.,Ltd. Address before: 213164 No.205, Fenglin South Road, Wujin national high tech Industrial Development Zone, Changzhou City, Jiangsu Province Patentee before: SHANGHAI ZHENHUA HEAVY INDUSTRY CHANGZHOU COATINGS Co.,Ltd. |